Production and utilization of magnesium chlorid



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@uw www5 UNITED sTATEs PATENT oEEIoE.

GEORGE HERBERT BAILEY AND GLYN WILLIAM ARNOLD EosTEE., or LONDON, ENGLAND, AssIeNoEs TO THE BRITISH ALUMINIUM COMPANY LIMITED, OE

LONDON, ENGLAND.

PRODUCTION AND IITILIZATION OF MAGNESIUM CHLORID.

i Specication of vLetters Patent.

Patented Feb. 24, 1920.

'Application led September 29,1917.. Serial No. 194,076.

linvented certain new and useful Improvements Relating to the Production and Utilization of Magnesium Chlorid, of which the following is a specification. y

This invention relates to the production and utilization of anhydrous magnesium chlorid; F

As magnesium chlorid occurs ordinarily in the hydrated form, it must, before being used for the production of magnesium, be

dehydrated. This dehydration is usuallyy Carried out by cautiously heating a double salt of the magnesium chlorid with ammonium chlorid.

The magnesium and ammonium salts are dissolved in water and carefully evaporated. The cake of mixed salts must then be very carefully dried before fusion. During the fusion,the ammonium chlorid is drivenv oli, the anhydrous magnesium chlorid remaining as a Lliquid The ammonium chlorid driven oli1 is diiiicult if not impossible to recover, and there is always a certain amount 'of decomposition of the magnesium chlorid. 4The process is also ver tedious and costly.

The electrolysis o" magnesium chlorid, and the regeneration of t e electrolyte by causing the chlorin liberatedl at the anode to re-act on magnesia roducing magnesium chlorid and giving o well known, and we do not claim such processes broadly. In the processes hitherto proposed, the interaction of the liberatedb chlorin and magnesia is not complete, and provision is made for the escape to the atmosphere of lpart of the chlorin liberated in the electrolytic bath, necessitating periodical interruptions of the process for further supplies of ma nesium chlorid to the cell.

he' principal object of this invention therefore is to greatly simplify and cheapen the production of `anhydrous magnesium chlorid by avoiding the use of aqueous solu- B. Se., a A

carbon monoxid are A tions, and further to employ Waste gases containing chlorin in its production.

A further object of the invention is to provide for the continuous working of the electrolytic process for the production of magnesium and alloys thereof from magnesia or magnesite.

The invention consists broadly in treating in suitable apparatus, a mixture of magnesia' and carbon with chlorin continuously supplied from an external source at a suitable temperature for the production of anhydrous magnesium chlorid.

The invention further consists'in treating the mixture of magnesia and carbon with waste gases containing chlorinl and practically free` from oxygen at a suitable vtemperature for the production of anhydrous magnesium chlorid.

The invention further consists in preparing magnesia in a porous form, suitable for treatment by chlorin or waste gases con-s tainingchlorin for use in the production of anhydrousk magnesium chlorid, by preparing blocks or briquets of a mixture of magnesitev and carbon'land baking the said blocks at a high temperature so as to drive olf carbon dioXid/gas.

The invention also consists in a process either for the production of anhydrous magnesium chlorid or for the electrolysis of magnesium chlorid in which, when used for electrolysis, a mixture of magnesia 'and car- -bon is acted upon in a reaction retort` connected with, but separate from the electrolytic cell, at a suitable temperature by the chlorin set free at the anode; and the molten magnesium chlorid thereby produced passes into the electrolytic bath to maintain the composition of the electrolyte practically constant; and in which, when used for the production of the said chlorid, a supply of chlorin from an external source (preferably waste gases containing chlorin) is supplied to the said miiture of magnesia and carbon,- the electrolytic bath and thefreaction retort being maintained at their respective optimum temperatures. The said process is started so as to produce anhydrous magnesium chlorid, and can be changed practically instantaneously to eiect electrolysis of the said chlorid, means being provided to supply chlorin to the reaction retort either from the anode chamber of the electrolytic bath or from the external source as desired.

The invention further consists in the ap.

the'reaction expressed by the said equation being well known from a very early date.4 1t is preferable, however, that the carbon shall be somewhat in excess. Thus, 84 parts of magnesite (or 40 parts of magnesia) are intimately mixed with 12 parts of carbon, or suitable carbonaceous matter. The finely ground mixture of magnesite and carbon is Well mixed with tar and pitch in suitable proportions, and pressed into blocks or briquets. These blocks are then baked at high temperature, about 1000o C. to 1200 C., provision being made by excluding air to prevent the carbon in the mixture burning away. During the baking,the magnesite in the blocks gives up carbon dioxid. This renders 'the blocks porous, and in a condition very suitable for the subsequent action of the chlorin.

. The resulting magnesia-carbon blocks cooled out of contact with air are broken into lumps of a suitable size, and placed in `a vertical or inclined retortheated to about 7 50 C. to 800 C. which is appreciably higher than the optimum temperature, 650 C. to 700o magnesium chlorid. Chlorin gas, preferably7 dry, passes into this retort absorbed by the carbon magnesia mixture.

The magnesium chlorid formed is, atthe temperature of reaction, liquid, 'and flows down the retort to the bottom, where it is either collected or is allowed to run direct into lan electrolytic cell; lThe carbon monis burnt or otherwise disposed of. The carbon monoxid may be used as fuel for baking the magnesite carbon blocks, or for heating the reaction retort, or for heating the electrolytic bath.

v It is /found that under reasonable and practical conditions the reaction proceeds so readily and with such completeness that all chlorin is taken up to form' anhydrous magnesium chlorid. The process can thus, be used. for the removal of chlorin from waste gases, such as those arising from the production of bleaching powder. The said waste gases should be practically free from oxygen.f v

Alternativelyto coolingdown after bak- 'of non-conducting metal e to be alloyed with the magnesium,

C., for the electrolysis fof.-

and is completely oxid escapes from the top of the retort, and I Referring now to the accompanying ldrawings Figure l illustrates an electrolytic cell in vconnection with which is a tube or reaction retort in which regeneration of the electrolyte is provided for according to this invention, and f Fig. 2 illustrates an l'alternative form of the same with which the baking oven for the magnesite carbon briquets is combined.

ln carrying the invention into effect for the production of magnesium in this example where the production of magnesium chlorid is made a part of the process of elec.-

trolysis, the decomposition cell a is a conven1ently shaped tank of steel or other suitable material, protected from oxidation and corrosion by suitable linings, e. g., a lining of firebrick. An inclined tube or retort b of the -same material as the tank is provided as a branch from its upper part, and is protected against 'corrosion by a lin ing of-rebrick. The tank and'retort are built into a suitable setting c, so that they can be maintainedat a temperature between KOU-9C. .and 800 C., preferably' by-gas firing. Within the tank is placed a crucible d material; containing the say aluminium. ,Electrical connection with the metal e is obtained by means of a graphite rod f which is protected where it passes through the electrolyte by the sleeve g of insulating material. The tank also contains the graphite electrode la., which forms the anode, and is inclosed, as shown, by the bell z', constructed of insulating material. The tank a and retort b are connected by the pipe lo, which thus conveys the chlorin liberated atthe anode k to the retort b. The

tank and retort are filled to the level shown with the molten electrolyte, composedA of a mixture of anhydrous magnesium chlorid.

and sodium chlorid in-suitable proportions,

with or without potassium chlorid. The I is charged with lumps of carbon-magnesia mixture Z. Thev chlorin from the anode chamber z' is taken up by this mixture with the formation o'f anhydrous magnesium chlorid whichiows down into the electrolyte`enrichingfthe latter just Where it is wanted, e., 1n the region about the cathode I lpart of the retort, b, above the electrolyte able for collecting, in the usual way, magnesium which. floats on the surface of the electrolyte.

In working, as the magnesia carbon mixture in the retort melts away under the infiuence of the chlorin', fresh mixture is fed into the upper end of the retort.` The process is thus continuous, the material fed in being magnesia and carbon (obtained from magnesite and carbon) the end products being magnesium or its alloys, and carbon monoxid, which is led -oi' and either utilized `or burnt. As. the absorption of chlorin in the retort is complete and' the amount of. chlorin given od at the anode is equivalent to the amount of magnesium withdrawn from the bath, it follows that exactly as much magnesium chlorid is returned to the bath from the retort as is decomposed by the current. The strength of the bath thus remains constant.

` We find that, using a separate electrolytic cell and reaction retort and specially prepared magnesia carbon blocks as above described, the absorption of chlorin4` in the reaction retort is quite com leteunder suitable conditions, no trace of chlorin being Vfound in the escaping carbon monoxid gas. We have however failed to achieve anything approaching such a result when attempting the process with lnagnesia carbon blocks placed in the electrolytic bath in a known manner.

In the said known mannery of producing magnesium chlorid by electrolysis, rovision is, in fact, made for the escape of c lorin.

Alternatively, the bakin of the magnesite carbon briquets may be e the magnesite-carbon briquets being fed first into a heating zone or baking retort, in which the vcarbon dioxid is driven o, and then, without cooling down, into the reaction retort or z-one in which they are treated with chlorin or chlorin containingv gases." Fig. 2 shows the said modified form "of the apparatus. The tube or reaction retort b is provided with or suitably connected t0 the baking tube b', into which the magnesite carbon briquets l are fed through a movable door, hopper, or the like, and which may be provided with known means to prevent the escape of gases therefrom when opened to ad' mit the briquets. A pipe k? is provided for theescape of carbon dioxidgas. A pipe Ic is provided for the escape' of'carbon monoxid` gas from the reactign retort b. l 'Valves s suitably adjusted `may be provided in con- 4nection with the pipes llc land k2 for regulatingthe pressure of the escaping gases'.

he gases after heating the baking tube may be led around the reaction retort, and thence around the electrolytic cell; diminishing temperatures being required at these three .'places as hereinbefore stated. The

v j i ected in a modilfied form of the apparatus abovedescribed,

three said parts may however be independently gas heated, provision for such heating being indicated in the drawing. The gas supply may be controlled by valves lv, and, after the process is started, carbon monoxid escaping from the reaction retortv may be used for the-said heating.

\ The same a paratus may be used eitherfor the electrolytic production of magnesium or its alloys or for the production of anhydrous magnesium chlorid. In the latter case the tank a serves as a collecting vessel for the liquid magnesium chlorid; the crucible d, electrodes f and h, insulating sleeve g and bell z' being removed. Also as in our invention the electrolytic production of magnesium or its alloys is effected, after the process isfairly. started with practically no further supply of chlorin from an external source, a three-way valve or its equivalent may be provided at V', so as to allow the chlorin to pass either from the electrolytic bath or from the external source of supply into the reaction retort b, as desired.

Having now fully described and ascer tained our said invention and the manner in which it is to be performed, we declare that what we claim is 1. A process for producing `anhydrous magnesium chlorid, consisting 1n treatingat;

a suitable temperature a `mixture of mag nesia and carbon in porous form with chlorin, or a gaseous mixture containing chlorin continuously su plied from an external source and practica ly free from oxygen, and allowing the liquid chlorid to flow of.

2. A process for producing. anhydrous magnesium chlorid, consistingl mixing finely divided magnesite and carbon witlra suitable tar mixture, briqueting the ma baking the briquets at a suitable temperature in a neutral or reducing atmosphere to drive oli? carbon dioxid and render tliem porous, and acting on the baked magnesia-carbon briquets or fragments thereof at a suitable temperature with chlorine gas or a gaseous mixture containing chlorin and practically free from oxygen.

3. A process for ciable loss of'chlorin,l consisting in treating with chlorin a porous coherent mixture of magnesia and carbon maintained at a suitable temperature in a reaction retort allowing the liquid chlorid to flow olf from the said mixture into the electrolytic cell, main! the production of anhydrous magnesium chlorid and the simulta- .'neous electrolysis thereof with no appremagnesium chlorid, thesteps which consist in heating briquets contaming magnesite pel carbon dioxid, and thereafter reacting With chlorin upon the heated briquets.

E. In a process of producing anhydrous 5 magnesium chlorid, the steps which consist in heating briquets containin carbon to a temperature su carbon dioxid, and feeding thel resulting porous and highly heated briquets into anv atmosphere containing' chlorin.

In testimony whereof We have signed our names to this specication.

GEORGE HERBERT BAILEY. GLYN WILLIAM ARNOLD FOSTER. 

